NANOCATALYSTS

ADEM YILDIRIM
UNAM-Institute of Materials Science and Nanotechnology
MSN 532: Selected Topics in Materials Science and Nanotechnology
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Outline
Catalysis
Types of Catalysts
Examples of Heterogeneous Catalysis

Nanocatalysis
Preparation
Size Effects
Shape Effect
Support Materials

Some Recent Advances
Nanocatalyst Preparation
Silica Supports
Carbon Supports

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Catalysis
The catalyst accelerate the rate of a chemical reaction
(A B) without itself being consumed in the process.
Catalysts generally react with one or more reactants to form
intermediates that subsequently give the final reaction
product, in the process regenerating the catalyst.

Y + X XY

(1) X + C XC
(2) Y + XC XYC
(3) XYC CZ
(4) CZ C + Z
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Types of Catalysts
Homogeneous catalysts
Homogeneous catalysts function in the same phase as the
reactants.



Heterogeneous catalysts
Heterogeneous catalysts are those which act in a different
phases than the reactants.
Heterogeneous catalysts are generally solids that act on
substrates in a liquid or gaseous reaction mixture.
Most nanocatalysts are heterogeneous catalysts for example
metal nanoparticles.

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Hydrogenation
On solids, the accepted mechanism today is called the Horiuti-
Polanyi mechanism.
1. Binding of the unsaturated bond, and hydrogen dissociation
into atomic hydrogen onto the catalyst
2. Addition of one atom of hydrogen; this step is reversible
3. Addition of the second atom; effectively irreversible under
hydrogenating conditions.
Examples of Heterogeneous Catalysis
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Examples of Heterogeneous Catalysis
Catalytic convertor
A catalytic converter is a device
used to reduce the toxicity of
emissions from an internal
combustion engine.


2CO + O
2
2CO
2
2NO
x
xO
2
+ N
2
C
x
H
2x+2
+ [(3x+1)/2]O
2
xCO
2
+ (x+1)H
2
O
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Nanocatalysis
Nanocatalysis research can be explained as the
preparation of heterogeneous catalysts in the
nanometer length scale.
They are very promising and it can be expected
that use of nanocatalysts can decrease the
energy usage in the chemical processes results
in a greener chemical industry.
Also they can be used for water and air cleaning
processes and new generation fuel cells.
However, these new features come with new
problems like, thermal stability and separation
after reaction completed.
Parameters like surface area, activity,
selectivity, longevity, and durability must be
well characterized.

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Nanocatalysis
Size Effects
Technical catalysis has been concerned with small particles for a
long time.
The initial incentive to reduce the size of the particles of active
components was to maximize the surface area exposed to the
reactants, and thus minimize the specific cost per function.
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Shape Effect
The shape of the nanoparticle determines surface atomic arrangement
and coordination.
For example, studies with single-crystal surfaces of bulk Pt have shown
that high-index planes generally exhibit much higher catalytic activity
than that of the most common stable planes, such as {111}, {100}, and
even {110}.
Because the high-index planes like; {210}, {410} and {557} have a high
density of atomic steps, ledges, and kinks, which usually serve as
active sites for breaking chemical bonds.



Nanocatalysis
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Nanocatalysis: Preparation
1. Solution Method:
Metal nanoparticles (Pd, Au, Co, Pt so on) are generally prepared by
reduction of organometallic compound solutions in the presence of
surfactant molecules.
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Nanocatalysis: Preparation
2. Vapor Deposition and Lithographic Methods:
Titania-supported Au Gold atoms on the (100) surface of Ni
These methods are expensive and production of large amounts of
catalyst is impossible and they are only used for kinetic studies and to
identify the size and shape effects for metal nanoparticle catalysts.
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Nanocatalysis: Supports
Mesoporous Materials
Mesoporous
Silicas
In designing and
synthesizing new solid
inorganic catalysts
the aims are to maximize
surface area, activity,
selectivity, longevity, and
durability.


A mesoporous material is a
material containing pores with
diameters between 2 and 50 nm.
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Nanocatalysis: Supports
Examples
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Some Recent Advances in
Nanocatalysis
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They describe a method for the synthesis of tetrahexahedral (THH) Pt NCs
at high purity. The THH shape is bounded by 24 facets of high-index planes
~{730}.

Size of particles can be tuned between 20-200 nm by simply changing the
reaction time.


Preparation of new NCs
Size control of THH Pt NCs and their thermal stability.
SEM images of THH Pt NCs grown at (A) 10, (B) 30, (C) 40, and (D) 50 min.
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Characterization of Tubes
Structure and stability.
Preparation of new NCs
They found tetrahexahedral PT particles nearly 2 fold active than the spherical
ones
Particles are stable up 850
0
C
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Preparation of new NCs
For metals important in catalysis and other nanotechnological fields,
synthesis by using nanoporous polymer and anodic aluminum films as
templates led to gold, nickel and palladium nanotubes, but with inner
diameters as large as 10100 nm.

This fact seems to suggest that thin-walled metal nanotubes with
diameters below 10 nm might be unobtainable because of their extremely
high surface energies.

They demonstrate the first synthesis of platinum, palladium, and silver
nanotubes, with inner diameters of 34 nm and outer diameters of 67 nm,
by the reduction of metal salts confined to lyotropic mixed LCs of two
different sized surfactants.



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In the typical fabrication process, the liquid crystalline phase of hexachloro
platinic acid (H
2
PtCl
6
), nonaethylene glycol monododecyl ether (C
12
EO
9
),
polyoxyethylene sorbitan monostearate (Tween 60) and water at a molar ratio of
1:1:1:60 was treated with hydrazine.
Preparation of Particles
Preparation of new NCs
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TEM images of A) platinum, B) palladium nanotubes
Characterization of Tubes
Structure.
Preparation of new NCs
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The role of each component in these catalysts, metal particles, oxide
supports, and their interface must be understood, requiring not only catalyst
synthesis but characterization and performance in designated catalytic
reactions. (reactivity studies)

Parameters to control in transition metal heterogeneous catalysts include;
-Particle composition, Size and shape, Support composition and pore size
distribution, Organizational structure of the porous network.

They introduce a synthetic procedure to generate hexagonal structures
(SBA15) in neutral pH conditions in the presence of Pt nanoparticles.
Silica Supports
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Characterization of Particles
Structure.
TEM images of Pt/SBA-15 catalysts. (a) 1.7 nm, (b)
2.9 nm, (c) 3.6 nm, and (d) 7.1 nm. The scale bars
represent 40 nm.
Silica Supports
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Catalytic Activity.
Ethylene Hydrogenation Turnover Rates and Kinetic Parameters on Pt Catalysts
Silica Supports
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Silica Supports
Colloidal nanoparticles are usually prepared in the presence of organic capping
agents, such as polymers or surfactants, that prevent the aggregation of
nanoparticles in solution.

At high temperatures, typically above 300
0
C, however, the organic capping
layers can decompose and the metal nanoparticles can deform and aggregate.

Many industrially important catalytic processes, including CO oxidation, partial
oxidation and cracking of hydrocarbons and combustion reactions, are carried out
at temperatures above 300 C.

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The Pt@mSiO2 coreshell nanoparticles were prepared by polymerizing the silica
layer around the surface of Pt nanoparticles using a sol gel process.

To a pH 10-11 solution of TATB caped Pt Nanoparticles, a controlled amount of 10
vol% TEOS diluted with methanol was added to initiate the silica polymerization.

The as-synthesized Pt@SiO2 was calcined at 350 C or higher for 2 h in static air
to remove TTAB surfactants to generate Pt@mSiO2 particles.
Silica Supports
Preparation of Particles
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Characterization of Particles
Structure.
TEM image of Pt nano crystals Thermal stability of Pt@mSiO2 nanoparticles. TEM
images of Pt@mSiO2 nanoparticles after calcination
at 350
0
C (a,b), 550
0
C (c) and 750
0
C (d).
Silica Supports
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CO oxidation as a model reaction.

The design of Pt@mSiO2 coreshell
nanoparticles enables the direct
access of reactive molecules to the
catalytically active core metals.

The activity of the Pt@mSiO2
catalyst was as high as that of TTAB-
capped Pt nanoparticles.


Catalytic Activity of Particles
Silica Supports
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Carbon Supports
Mesoporous carbons (OMC) are obtained by nanocasting from ordered
mesoporous silica as a mould.

Porous carbon materials combine chemical inertness, biocompatibility, and
thermal stability, and are thus suitable for many different applications.

Carbons are notoriously difficult to separate from solutions. Magnetic silica
gel can be synthesized by entrapment of magnetite particles in the forming gel.



In the case of carbon, the resulting material has typically surface areas of
around 600 m
2
g
-1
and a pore volume below 0.2 cm
3
g
-1
.


Magnetic
separation
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(1) Selective deposition of magnetic nanoparticles,
(2) Protection of the nanoparticles by a nanometer thick carbon layer.
(3) Subsequent introduction of the catalytically active component.
Illustration of the synthesis procedure
A) ordered mesoporous
silica SBA-15; B) carbon/SBA-15
composite; C) B with surfacedeposited
cobalt nanoparticles; D) protected
cobalt nanoparticles on C; E) magnetic-
ordered mesoporous carbon; F) Pd on E.
Preparation of Particles
Carbon Supports
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Carbon Supports
Characterization of Particles
Structure.
TEM images of CoOMC at different magnification: a) low magnification; b) high magnification.
Arrows indicate hollow carbon shells left after the leaching procedure.
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After the addition of CoOMC to the Rh6G-containing solution, there
was a change from orange-red to colorless within minutes.
Carbon Supports
Characterization of Particles
Magnetic Separation.
Rh6G aqueous solution (left) and after adsorption of the Rh6G on Co
OMC and separation of the dye loaded CoOMC by a magnet (right).
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The catalyst was used as a slurry in a small, well-stirred reactor that
had a continuous supply of hydrogen, and the hydrogen consumption
was monitored.
Catalytic Activity.
Carbon Supports
Hydrogenation of octene over 1% Pd-loaded CoOMC. Fist run, second run after
separation of catalyst and new addition of octene, run to test how separable the catalyst
is after magnetic removal of catalyst and readmission of hydrogen.
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Carbon Supports

Layer-by-layer (LbL) self-assembly approach, which enables the fabrication
of many different core-shell materials.
- Silicas, titanias, polymers, silica polymer nano composites, magnetic
materials.
- Solid core spheres or hollow core spheres may be produced, depending on
core template removal.

They report on the fabrication of new silica templates with a solid silica
core/mesoporous shell, containing an Au nanoparticle within the silica core.
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Preparation of Particles
Carbon Supports
Schematic Illustration for the Synthesis of Au@HCMS Polymer and Carbon Capsules
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Characterization of Particles
Structure.
Carbon Supports
Characterization of Au@SCMS silica templates with core diameter of 80 nm and shell thickness
of 25 nm: (a) SEM image, (b) TEM image, and (c) N2 adsorption/desorption isotherms and the
corresponding pore size distribution (inset).
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Characterization of Particles
Structure.
Carbon Supports
TEM image of (a) Au@HCMS polymer capsules with core diameters of 50 nm and
shell thicknesses of 15 nm. (b) Au@HCMS carbon capsules with core diameters of
80 nm and shell thicknesses of 25 nm.
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Conclusion
Size and shape controlled preparation of metal
nanoparticles are very promising for greener
heterogeneous catalytic reactions.

Size and shape effects of the particles, the kinetic
pathways and selectivity of the particles must be
completely understood.

Support materials for these nanocatalysts must be well
studied and role of them and their interfaces in the
catalysis must be understood.
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